DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 23 June 2025 has been entered.
Claim Status
Claims 1, 2, 5-10, 16, 17, 22, 24, and 28 are amended. Claims 41-43 are new. Claims 3, 4, 11-15, 17-21, 26, 27, and 30-36 are cancelled.
While legible and proper, the claims as filed on 23 June 2025 are a bit blurry from the faxing method. Applicant’s Representative kindly provided a clean copy to the Examiner, which is attached to this Action for reference.
Claims 1, 2, 5-10, 16, 17, 22-25, 28, 29, and 37-43 are pending for examination below.
Response to Arguments
Applicant’s arguments and amendments filed 23 June 2025 have been fully considered. Some are persuasive and some are not, as explained below.
Applicant’s arguments and amendments with respect to the rejection(s) of claim(s) 1, 2, 5-9, 16, 17, 22, 24, 28, 29, and 37-40 under USC 102 or USC 103 over Suriye or Chen ‘568 in view of Khanmamedova have been fully considered and are persuasive. Suriye teaches tin in an amount of 0.005 to 2 wt%, which is not within the range of 3 to 15 wt% of amended independent claims 22, 24, and 28. Suriye also requires a Group 8-10 metal in an amount of 0.1 to 5 wt%, which does not meet the limitation of less than 0.1 wt% Groups 8-10 or chromium metal of amended independent claim 16. Therefore, the rejections have been withdrawn. However, upon further consideration, a new ground(s) of rejection is made in view of a new interpretation of previous prior art in combination with newly discovered prior art in view of the amendments.
Applicant's arguments with respect to the rejection of claim 10 over Khanmamedova or claims 22-25, 28, and 39 over Heckelsberg in view of Chen ‘406 have been fully considered but they are not persuasive.
Applicant argues that Khanmamedova does not teach the newly added selectivity of at least about 55 wt% C2-C4 olefins, because Khanmamedova merely refers generally to the conversion of light paraffins to olefins and/or aromatics.
In response, the Examiner agrees that Khanmamedova is no longer a 102 rejection for claim 10, however, Khanmamedova renders obvious newly amended claim 10. Claim 10 as amended requires a process of contacting a feed comprising at least 20 vol% propane with a catalyst comprising the claimed metals in the claimed amounts, where the contacting converts the propane to olefins having C2-C4 carbon atoms with a selectivity of at least about 55%. Khanmamedova teaches the catalyst comprising a zeolite support having tin in an amount of 1.52 wt%, Group 6 or 7 metal, and Ge in an amount of 0.96 wt% (paragraphs [0027], [0054]). These are within the ranges of claim 10. Khanmamedova further generally teaches using the catalyst in a process for converting light paraffins to olefins (page 5, first column, (M)). One of ordinary skill in the art would understand that the term “light paraffins” generally includes at least one of C2, C3, and C4 paraffins, and one of ordinary skill in the art would easily select only (100%) C3 paraffins from this list, without undue experimentation and with a reasonable expectation of success, giving a feed which comprises more than 20 vol% propane as claimed. Khanmamedova further teaches the conversion takes place at about 425-760°C and a pressure of about 10 to about 2000 psi (page 5, first column, (M)) and the instant specification teaches the reaction conditions for the dehydrogenation and metathesis reaction include 500-650°C and a pressure of 1 to 100 bar (14.5 to 1450 psi) (instant specification paragraph [73]). Therefore, because Khanmamedova teaches reacting a similar catalyst with a feed which can comprise the claimed propane in the claimed amounts at similar conditions, one of ordinary skill in the art would reasonably expect the process to produce the similar result of the claimed selectivity to C2-C4 olefins of at least 55%, absent any evidence to the contrary. As such, Khanmamedova renders obvious newly amended claim 10.
Applicant argues in the second to last paragraph of page 10, the second to last paragraph of page 12, and the second to last paragraph of page 13 of the Remarks that Chen does not teach the newly added limitation of 3 to 15 wt% tin in claims 22, 24, and 28, as Chen teaches much smaller amounts (0.6 wt% and 0.57 wt%) in Examples 4 and 6.
In response, as noted by Applicant, the small amounts are exemplified amounts. However, Chen is not limited to exemplary teachings, but instead is used for all it teaches. Chen teaches the broad formula of a zeolite comprising tin in a mole fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Using molar mass to convert the mole fractions to weights, Chen teaches approximately 1.3 to 42.6 wt% tin in the zeolite. Chen additionally teaches that the total catalyst includes 0.01 to 5 wt% Pt (column 6, line 38) and 5 to 50 wt% alumina binder (column 6, line 67-column 7, line 1), which leaves 49.99 to 90 wt% zeolite. Thus, Chen teaches that the total catalyst comprises approximately 0.6 to 38.34 wt% tin, which overlaps the range of 3 to 15 wt%. Therefore, Chen continues to render obvious the catalyst comprising tin in the amount claimed.
Applicant also argues in the first full paragraph of page 11, the paragraph bridging pages 12-13, and the paragraph bridging pages 13-14 that Heckelsberg in view of Chen does not the amount of less than 0.1 wt% Groups 8-10 and chromium metal of newly added claims 41-43, because Chen requires platinum.
In response, the Examiner notes that while Chen requires a noble metal which could include platinum or multiple other Group 8-10 metals (column 6, lines 14-16), the amount of the noble metal is about 0.01 to about 5 wt% (column 6, lines 38-39), which overlaps the claimed amount of less than 0.1 wt%, rendering the claimed amount obvious. However, for purposes of compact prosecution, additional new prior art containing no Group 8-10 or chromium metal (0 wt%) is used to anticipate the range of less than 0.1 wt% in new claims 41-43 in the rejection below.
Claim Objections
Claim 1 is objected to because of the following informalities:
With regard to claim 1, the claim is dependent from claim 22 and recites the limitation “wherein tin is present in the dehydrogenation catalyst in an amount from about 3 wt% to about 15 wt%”. However, claim 22 as amended already recites this limitation as written. Thus, the recitation in claim 1 is redundant, and should be removed.
Appropriate correction is required.
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
Claim 10 is rejected under 35 U.S.C. 103 as being unpatentable over Khanmamedova et al. (US 2008/0293989).
With regard to claim 10, Khanmamedova teaches a catalyst comprising a zeolite support comprising tin in an amount of 1.52 wt% and Ge in an amount of 0.96 wt% (paragraph [0054]), which are with the ranges of about 1 to about 20 wt% and about 0.1 to about 6 wt%, respectively, of instant claim 10. Khanmamedova further teaches that an additional metal which is Group 6 or Group 7 can be deposited on the catalyst support (paragraph [0027]). This is equivalent to the dehydrogenation and metathesis catalyst of claim 10. Khanmamedova further generally teaches using the catalyst in a process for converting light paraffins to olefins (page 5, first column, (M)).
Khanmamedova does not specifically teach i) the light paraffin feed is at least 20 vol% propane or ii) that the light paraffins are converted to C2-C4 olefins with a selectivity of at least 55 wt%.
With regard to i), Khanmamedova teaches light paraffins (page 5, first column (M)). One of ordinary skill in the art would understand that the term “light paraffins” generally includes at least one of C2, C3, and C4 paraffins, and one of ordinary skill in the art would easily select only (100 vol%) C3 paraffins (propane) from this finite list, without undue experimentation and with a reasonable expectation of success, giving a feed which comprises more than 20 vol% propane as claimed.
With regard to ii), Khanmamedova further teaches the conversion takes place at about 425-760°C and a pressure of about 10 to about 2000 psi (page 5, first column, (M)) and the instant specification teaches the reaction conditions include 500-650°C and a pressure of 1 to 100 bar (14.5 to 1450 psi) (instant specification paragraph [73]). The conditions of Khanmamedova overlap the claimed conditions. Therefore, because Khanmamedova teaches reacting a similar catalyst comprising the claimed dehydrogenation and metathesis metals with a feed which can comprise the claimed 20 vol% propane at similar conditions including temperature and pressure, one of ordinary skill in the art would reasonably expect the process of Khanmamedova would also function as a dehydrogenation and metathesis process which would provide the claimed selectivity to C2-C4 olefins of at least 55%, absent any evidence to the contrary.
Claim 16 is rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Suriye et al. (WO 2018/108544).
With regard to claim 16, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a combined dehydrogenation-disproportionation catalyst in a physical mixture (column 1, lines 49-54 and column 2, lines 41-45). Heckelsberg further teaches that the dehydrogenation catalyst comprises copper on alumina (column 1, lines 55-58). While Heckelsberg also contemplates mixtures of metals, Heckelsberg contemplates the single metal being copper (Group 11 metal). When the catalyst comprises only copper as the metal, the catalyst comprises Cr and Groups 8-10 metals in an amount of 0 wt%, which is within the range of less than about 0.1 wt% of instant claim 16. Heckelsberg additionally teaches that the disproportion catalyst can comprise tungsten (Group 6 metal) on silica (solid support metal oxide) and can be any catalyst active at temperatures of 800°F or higher (column 2, lines 1-3).
Heckelsberg fails to teach the metathesis catalyst further comprises Zeolite Y in the support.
Suriye teaches a process for dehydrogenation and metathesis of alkanes (paragraphs [010] and [017]). Suriye teaches that the metathesis catalyst comprises a transition metal which is tungsten (paragraph [018]) on a support comprising a mixture of silicon dioxide (silica) and zeolite Y (paragraphs [019]-[020]). Suriye does not specifically teach how much of the second composition is the zeolite Y. However, one of ordinary skill in the art would understand the choice of the amount of zeolite Y would affect the total acidity of the support, which can affect the conversion and selectivity of the process. Thus, the amount of zeolite Y is a process parameter which can be optimized. It would have been obvious to one having ordinary skill in the art to have determined the optimum value zeolite Y of an amount of 1 to 20 wt% of the metathesis catalyst, as claimed, through routine experimentation in the absence of a showing of criticality. See MPEP 2144.05(II). Suriye additionally teaches that the process comprising the metathesis catalyst having a zeolite Y and silica support with the transition metal provides additional selectivity for the reaction of propane to the desired olefins product comprising C2 and C4 olefins (paragraph [050]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the metathesis catalyst of Suriye in the process of Heckelsberg, because Heckelsberg and Suriye each teach a process comprising dehydrogenation and metathesis of propane to produce olefins, Heckelsberg teaches the disproportionation (metathesis) catalyst comprises tungsten oxide on a silica support and can include any catalyst active at a temperature of 800°F or higher, and Suriye teaches the metathesis catalyst comprising tungsten oxide, silica, and zeolite Y is used at a temperature of 450-650°C (842 to 1202°F) (paragraph [045]) which is within the range of 800°F or higher and further teaches that the catalyst comprising zeolite Y and silica support with the transition metal provides additional selectivity for the reaction of propane to the desired olefins product comprising C2 and C4 olefins (paragraph [050]).
Claim 17 is rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Suriye et al. (WO 2018/108544) as applied to claim 16 above, and further in view of Lee et al. (US 2017/0151553).
With regard to claim 17, Heckelsberg in view of Suriye teaches the process above.
Heckelsberg fails to teach the dehydrogenation catalyst comprising copper can additionally comprise tin in an amount of 3 to 15 wt%.
Lee teaches a process for dehydrogenation of propane to propene (paragraph [0001]) comprising a catalyst which includes 0.1 to 10 wt% tin (paragraph [0043]), which overlaps the range of about 3 to about 15 wt% of instant claim 17, rendering the range prima facie obvious. Lee further teaches that tin is a promotor which reduces catalyst deactivation rate and increases catalyst stability (paragraph [0042]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the tin in an amount of 0.1 to 10 wt%, as taught by Lee, because each of Heckelsberg and Lee teaches a process comprising dehydrogenation of propane over a dehydrogenation catalyst, and Lee teaches that adding tin as a promotor in an amount of 0.1 to 10 wt% reduces catalyst deactivation rate and increases catalyst stability (paragraph [0042]).
Claims 22-25, 28, 39, and 41-43 are rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Chen et al. (US 7,432,406).
With regard to claims 22 and 23, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a combined dehydrogenation-disproportionation catalyst (column 1, lines 49-54). When the feed is pure propane as described in Heckelsberg (column 3, line 75), the feed comprises 100 vol% propane, which is within the range of at least about 20 vol% of instant claim 22. Heckelsberg teaches that the disproportionation catalyst comprises tungsten or molybdenum (Group 6) on a support (column 2, lines 21-24). Heckelsberg teaches generally the concept of a dehydrogenation catalyst, and further teaches some examples of a dehydrogenation catalyst, but not limited to the examples (column 1, lines 54-56).
Heckelsberg is silent regarding a stannosilicate dehydrogenation catalyst comprising about 3 to about 15 wt% tin, where the tin is incorporated in the framework (instant claim 23).
Chen teaches a dehydrogenation process of paraffins having 2-30 carbon atoms (column 7, lines 41-42) comprising a catalyst including a zeolite comprising tin and silica (stannosilicate), where the tin is incorporated in the framework (instant claim 23) (column 1, lines 17-22). Chen teaches that the tin is included in the zeolite in a molar fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Using molar mass to convert the mole fractions to weights, Chen teaches 1.3 to 42.6 wt% tin in the zeolite. Chen additionally teaches that the total catalyst includes 0.01 to 5 wt% Pt (column 6, line 38) and 5 to 50 wt% alumina binder (column 6, line 67-column 7, line 1), which leaves 49.99 to 90 wt% zeolite. Thus, Chen teaches that the total catalyst comprises 0.6 to 38.34 wt% tin, which overlaps the range of 3 to 15 wt% of instant claim 22, rendering the range prima facie obvious. Chen further teaches that the catalyst comprising tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the dehydrogenation catalyst of Chen as the dehydrogenation catalyst of Heckelsberg, because each of Heckelsberg and Chen teaches a dehydrogenation catalyst for dehydrogenation of propane, and Chen teaches that the dehydrogenation catalyst having a zeolite incorporating tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
Heckelsberg in view of Chen does not explicitly teach the propane selectivity to C2-C4 olefins is at least about 55 wt%. However, Heckelsberg in view of Chen teaches a similar stannosilicate comprising tin in the framework in a similar amount, the same metathesis catalyst, and teaches the same dehydrogenation and metathesis process using the same feed comprising propane in an amount within the claimed range of at least 20 vol%. Thus, one of ordinary skill in the art would reasonably expect a similar result of selectivity to C2-C4 olefins of at least about 55 wt%, as claimed, absent any evidence to the contrary.
With regard to claims 24 and 25, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a combined dehydrogenation-disproportionation catalyst (column 1, lines 49-54). When the feed is pure propane as described in Heckelsberg (column 3, line 75), the feed comprises 100 vol% propane, which is within the range of at least about 20 vol% and the reaction is in an absence of an oxidizing agent, as claimed in instant claim 24. Heckelsberg teaches that the disproportionation catalyst comprises tungsten or molybdenum (Group 6) on a support (column 2, lines 21-24). Heckelsberg teaches generally the concept of a dehydrogenation catalyst, and further teaches some examples of a dehydrogenation catalyst, but not limited to the examples (column 1, lines 54-56).
Heckelsberg is silent regarding a stannosilicate dehydrogenation catalyst comprising about 3 to about 15 wt% tin, where the tin is incorporated in the framework (instant claim 25).
Chen teaches a dehydrogenation process of paraffins having 2-30 carbon atoms (column 7, lines 41-42) comprising a catalyst including a zeolite comprising tin and silica (stannosilicate), where the tin is incorporated in the framework (instant claim 25) (column 1, lines 17-22). Chen teaches that the tin is included in the zeolite in a molar fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Using molar mass to convert the mole fractions to weights, Chen teaches 1.3 to 42.6 wt% tin in the zeolite. Chen additionally teaches that the total catalyst includes 0.01 to 5 wt% Pt (column 6, line 38) and 5 to 50 wt% alumina binder (column 6, line 67-column 7, line 1), which leaves 49.99 to 90 wt% zeolite. Thus, Chen teaches that the total catalyst comprises 0.6 to 38.34 wt% tin, which overlaps the range of 3 to 15 wt% of instant claim 24, rendering the range prima facie obvious. Chen further teaches that the catalyst comprising tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the dehydrogenation catalyst of Chen as the dehydrogenation catalyst of Heckelsberg, because each of Heckelsberg and Chen teaches a dehydrogenation catalyst for dehydrogenation of propane, and Chen teaches that the catalyst having a zeolite incorporating tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
Heckelsberg in view of Chen does not explicitly teach the propane selectivity to C2-C4 olefins is at least about 55 wt%. However, Heckelsberg in view of Chen teaches a similar stannosilicate comprising tin in the framework in a similar amount, the same metathesis catalyst, and teaches the same dehydrogenation and metathesis process using the same feed comprising propane in an amount within the claimed range of at least 20 vol%. Thus, one of ordinary skill in the art would reasonably expect a similar result of selectivity to C2-C4 olefins of at least about 55 wt%, as claimed, absent any evidence to the contrary.
With regard to claims 28 and 39, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a physical mixture (catalyst system B instant claims 28 and 39) (column 2, lines 43-46) of a combined dehydrogenation-disproportionation catalyst in a single bed reactor (column 1, lines 49-54). When the feed is pure propane as described in Heckelsberg (column 3, line 75), the feed comprises 100 vol% propane, which is within the range of at least about 20 vol% of instant claim 28. Heckelsberg teaches that the disproportionation catalyst comprises tungsten or molybdenum (Group 6) on a support (column 2, lines 21-24). Heckelsberg teaches generally the concept of a dehydrogenation catalyst, and further teaches some examples of a dehydrogenation catalyst, but not limited to the examples (column 1, lines 54-56).
Heckelsberg is silent regarding a dehydrogenation catalyst comprising about 3 to about 15 wt% tin.
Chen teaches a dehydrogenation process of paraffins having 2-30 carbon atoms (column 7, lines 41-42) comprising a catalyst including a zeolite comprising tin (column 1, lines 17-22). Chen teaches that the tin is included in the zeolite in a molar fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Using molar mass to convert the mole fractions to weights, Chen teaches 1.3 to 42.6 wt% tin in the zeolite. Chen additionally teaches that the total catalyst includes 0.01 to 5 wt% Pt (column 6, line 38) and 5 to 50 wt% alumina binder (column 6, line 67-column 7, line 1), which leaves 49.99 to 90 wt% zeolite. Thus, Chen teaches that the total catalyst comprises 0.6 to 38.34 wt% tin, which overlaps the range of 3 to 15 wt% of instant claim 28, rendering the range prima facie obvious. Chen further teaches that the catalyst comprising tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the dehydrogenation catalyst of Chen as the dehydrogenation catalyst of Heckelsberg, because each of Heckelsberg and Chen teaches a dehydrogenation catalyst for dehydrogenation of propane, and Chen teaches that the catalyst having a zeolite incorporating tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
Heckelsberg in view of Chen does not explicitly teach the propane selectivity to C2-C4 olefins is at least about 55 wt%. However, Heckelsberg in view of Chen teaches a similar zeolite comprising Sn in a similar amount, the same metathesis catalyst, and teaches the same process comprising dehydrogenation and metathesis using the same feed comprising propane in an amount within the claimed range of at least 20 vol%. Thus, one of ordinary skill in the art would reasonably expect a similar result of selectivity to C2-C4 olefins of at least about 55 wt%, as claimed, absent any evidence to the contrary.
With regard to claims 41-43, Chen requires a noble metal which includes platinum, rhodium, rhenium, osmium, or iridium (all Group 8-10 metals) (column 6, lines 14-16). Chen further teaches the amount of the noble metal is about 0.01 to about 5 wt% (column 6, lines 38-39), which overlaps the claimed amount of less than 0.1 wt%, rendering the range prima facie obvious.
Claims 1, 2, 5 and 6 are rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Chen et al. (US 7,432,406) as applied to claim 22 above, and further in view of Sattler et al. (US 2021/0155565).
With regard to claims 1 and 2, Heckelsberg in view of Chen teaches the process above, where the catalyst comprises 0.6 to 38.34 wt% tin incorporated in the framework (instant claim 2) (column 1, lines 17-22), which overlaps the range of 3 to 15 wt% of instant claim 1, rendering the range prima facie obvious.
Heckelsberg in view of Chen fails to teach adding an additional metal which is Ir, Ga, Ag, or Au in an amount of 0.1 to 6 wt%.
Sattler teaches dehydrogenation of propane to propene in the presence of a small pore zeolite catalyst (paragraph [0028]) where the zeolite comprises Sn in the framework (paragraph [0031]) and about 0.1 to about 3 wt% catalytic metal (paragraph [0037]) where the catalytic metal is Ir, Ga, Ag, or Au (paragraph [0039]). This is within the range of about 0.1 to about 6 wt% additional metal of instant claim 10. Sattler further teaches that the catalyst also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to add the additional metal of Sattler to the catalyst in the process of Heckelsberg in view of Chen, because each of Chen and Sattler teaches a dehydrogenation catalyst for dehydrogenation of propane comprising tin in the framework, and Sattler teaches that the catalyst comprising tin in the framework and the additional metal which is Ir, Ga, Ag, or Au also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
With regard to claim 5, Heckelsberg teaches the metathesis catalyst comprises tungsten or molybdenum (column 2, line 22).
With regard to claim 6, Heckelsberg teaches a physical mixture of dehydrogenation catalyst and metathesis catalyst (column 2, lines 45-46).
Claims 7-9 are rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Chen et al. (US 7,432,406, Chen I herein) and Sattler et al. (US 2021/0155565) as applied to claim 1 above, and further in view of Chen et al. (US 6,566,568, Chen II herein).
With regard to claim 7, Heckelsberg in view of Chen I and Sattler teaches the method above comprising a physical mixture of catalyst (Heckelsberg column 2, lines 45-46).
Heckelsberg in view of Chen I and Sattler fails to teach i) multiple catalyst beds or ii) the amount of each of metathesis and dehydrogenation catalyst in a first and second bed
With regard to i), Chen II teaches a method for molecular averaging comprising a catalyst composition having both a conventional dehydrogenation catalyst and a conventional olefin metathesis catalyst (column 11, lines 36-39), where the conventional metathesis catalyst comprises preferably tungsten (instant claim 5) (column 12, lines 56-57). Chen II teaches that the catalyst can be a physical mixture of metathesis and dehydrogenation catalyst (column 15, Example 3), and further teaches that there can be one or more beds in the reactor (column 7, lines 62-64).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use multiple beds of catalyst in the process of Heckelsberg, as taught by Chen II, because Heckelsberg teaches the physical mixture of catalyst but does not explicitly teach multiple beds, and Chen II teaches that a physical mixture of dehydrogenation and metathesis catalysts can be used in one bed or more than one bed (column 7, lines 62-64), and one of ordinary skill in the art would find it obvious to select more than one bed as an option with a reasonable expectation of success from a finite list of options.
With regard to ii), Heckelsberg teaches that one of ordinary skill in the art can determine the optimum amount of disproportionation (metathesis) and dehydrogenation catalyst which is based on the catalysts chosen and their relative activities (column 2, lines 10-16). Thus, the amount of each catalyst in the catalyst bed is a result-effective variable, and can be optimized.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to optimize first bed to contain a portion of dehydrogenation catalyst and a portion of metathesis catalyst in any amount and to optimize the second bed to contain 95 wt% metathesis catalyst, because it has been held that discovering an optimum value of a result effective variable involves only routine skill in the art. See MPEP 2144.05(II).
With regard to claim 8, Chen teaches that the catalyst can be a physical mixture (column 15, Example 3) and also teaches that instead the catalyst can be in separate layers in a reactor (column 13, lines 54-56) or separate reactors (column 13, lines 56-58), each of which is equivalent to separate beds, as claimed. Thus, Chen teaches that selecting a physical mixture or separate beds are equivalent options. ,Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to select separate beds, as claimed, where separate beds is expected to be equally effective in the reaction process, and is selected from a finite list of options with a reasonable expectation of success.
With regard to claim 9, Heckelsberg in view of Chen does not specifically teach at least 3 alternating layers when the layers are present. However, selecting alternating layers is merely an option from a finite list of the arrangement of layers, which is either all the dehydrogenation layers followed by all the metathesis layers; all the metathesis layers followed by all the dehydrogenation layers; or alternating layers, and each has a reasonable expectation of success and can be selected without undue experimentation.
Claims 29, 37, and 38 are rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Chen et al. (US 7,432,406) as applied to claims 22, 24, and 28 above, and further in view of Suriye et al. (WO 2018/108544).
With regard to claims 29, 37, and 38, Heckelsberg in view of Chen teaches the method above, where the feed comprises a C3-C6 paraffin which can particularly be propane (column 1, lines 42-45) and the desired product comprises the disproportionated products of propene (column 1, lines 49-50) which are understood to be butene and ethylene.
Heckelsberg does not specifically teach that the feed can comprise a mixture of propane and butane.
Suriye teaches a process for metathesis and dehydrogenation of paraffins to olefins (paragraph [001]). Suriye further teaches the desired product is light olefins including butene and ethylene (paragraph [050]). Suriye additionally teaches the feed can comprise propane or a mixture of propane and butane (paragraph [043]). Thus, Suriye teaches that a mixture of propane and butane functions in the same manner a feed of propane with regard to forming the desired product.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use a feed comprising a mixture of propane and butane as the feed of Heckelsberg, because Heckelsberg teaches a C3-C6 paraffin which is preferably propane and the desired products include ethylene and butene, and Suriye teaches that a mixture of propane and butane produces the same desired butene and ethylene (paragraph [043]).
With regard to claim 40, Suriye does not teach the specific amount of propane and butane present when the feed is a mixture. However, when faced with a composition of two components, one of ordinary skill in the art would reasonably conclude that it would be obvious to try using equal parts, which is 50 vol% propane and 50 vol% butane, absent evidence of unexpected or surprising results. Case law holds that "[h]aving established that this knowledge was in the art, the examiner could then properly rely... on a conclusion of obviousness, 'from common knowledge and common sense of the person of ordinary skill in the art without any specific hint or suggestion in a particular reference.'" In re Bozek, 416 F.2d 1385, 1390, 163 USPQ 545, 549 (CCPA 1969). Thus, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to try a combination of equal parts propane and butane without undue experimentation and with a reasonable expectation of success. The amount of 50 vol% propane is within the ranges of about 30 vol% to about 85 vol% of instant claim 40.
Claims 22, 23, 24, 25, 28, and 41-43 are rejected under 35 U.S.C. 103 as being unpatentable over Heckelsberg et al. (US 3,445,541, cited on IDS of 01/18/2024) in view of Sattler et al. (US 2021/0155565) and Chen et al. (US 7,432,406).
With regard to claims 22, 23 and 41, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a combined dehydrogenation-disproportionation catalyst in a single bed reactor (column 1, lines 49-54). When the feed is pure propane as described in Heckelsberg (column 3, line 75), the feed comprises 100 vol% propane, which is within the range of at least about 20 vol% of instant claim 22. Heckelsberg teaches that the disproportionation catalyst comprises tungsten or molybdenum (Group 6) on a support (column 2, lines 21-24). Heckelsberg teaches the general dehydrogenation catalyst, and further teaches some examples of a dehydrogenation catalyst (column 1, lines 54-56).
Heckelsberg is silent regarding i) the dehydrogenation catalyst being a stannosilicate comprising tin (instant claim 23) and comprising less than 0.1 wt% Groups 8-10 metals (instant claim 41), ii) the amount of tin in the stannosilicate catalyst, and iii) the propane selectivity of the process to C2-C4 olefins.
With regard to the catalyst being a stannosilicate comprising tin i), Sattler teaches dehydrogenation of propane to propene in the presence of a small pore zeolite catalyst (paragraph [0028]) where the zeolite comprises Sn in the framework (stannosilicate instant claim 23) (paragraph [0031]) and a catalytic metal (paragraph [0037]) where the catalytic metal can be Ag, Au, Mo, W, Re, Zn, Cr, Mn, Ce, or Ga (paragraph [0039]). When the metal is selected from these metals, the catalyst comprises 0 wt% Groups 8-10 metals, which is within the range of less than 0.1 wt% of instant claim 41. Sattler further teaches that the catalyst also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the dehydrogenation catalyst of Sattler in the process of Heckelsberg, because each of Heckelsberg and Sattler teaches a dehydrogenation catalyst for dehydrogenation of propane, and Sattler teaches that the catalyst comprising tin in the framework and the additional metal also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
With regard to the amount of tin ii), Chen teaches a dehydrogenation process of paraffins having 2-30 carbon atoms (column 7, lines 41-42) comprising a catalyst including a zeolite comprising tin incorporated in the framework (column 1, lines 17-22). Chen teaches that the tin is included in the zeolite in a molar fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Chen further teaches that the catalyst comprising tin in the framework in this amount has increased selectivity and conversion (column 9, lines 22-24).
Using molar mass to convert the mole fractions to weights, Chen teaches 1.3 to 42.6 wt% tin in the zeolite. Sattler teaches that the catalyst comprises 2 to 80 wt% binder (paragraph [0067]) and 0.1 to about 3 wt% catalytic metal (paragraph [0037]), where the 17 to 97.9 wt% remaining is the zeolite. Thus, using the amounts of Chen, the catalyst of Sattler can comprise 0.2 to 41.7 wt% tin, which overlaps the range of 3 to 15 wt% of instant claim 22, rendering the range prima facie obvious.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the amount of tin in the catalyst of Chen for the catalyst of Sattler, because each of Heckelsberg and Chen teaches a dehydrogenation catalyst comprising platinum on a support for dehydrogenation of propane, and Chen teaches that the catalyst having a zeolite incorporating tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
With regard to the selectivity iii), Heckelsberg in view of Chen does not explicitly teach the propane selectivity to C2-C4 olefins is at least about 55 wt%. However, Heckelsberg in view of Sattler and Chen teaches a similar dehydrogenation catalyst comprising tin in the framework in a similar amount, the same metathesis catalyst, and teaches dehydrogenation and metathesis using the same feed comprising propane in an amount within the claimed range of at least 20 vol%. Thus, one of ordinary skill in the art would reasonably expect a similar result of selectivity to C2-C4 olefins of at least about 55 wt%, as claimed, absent any evidence to the contrary.
With regard to claims 24, 25, and 42, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a combined dehydrogenation-disproportionation catalyst (column 1, lines 49-54). When the feed is pure propane as described in Heckelsberg (column 3, line 75), the feed comprises 100 vol% propane, which is within the range of at least about 20 vol% of instant claim 24 and is in the absence of oxygen, as claimed. Heckelsberg teaches that the disproportionation catalyst comprises tungsten or molybdenum (Group 6) on a support (column 2, lines 21-24). Heckelsberg teaches the general dehydrogenation catalyst, and further teaches some examples of a dehydrogenation catalyst (column 1, lines 54-56).
Heckelsberg is silent regarding i) the dehydrogenation catalyst being a stannosilicate comprising tin (instant claim 25) and comprising less than 0.1 wt% Groups 8-10 metals (instant claim 42), ii) the amount of tin in the stannosilicate catalyst, and iii) the propane selectivity of the process to C2-C4 olefins.
With regard to the catalyst being a stannosilicate comprising tin i), Sattler teaches dehydrogenation of propane to propene in the presence of a small pore zeolite catalyst (paragraph [0028]) where the zeolite comprises Sn in the framework (stannosilicate instant claim 25) (paragraph [0031]) and a catalytic metal (paragraph [0037]) where the catalytic metal can be Ag, Au, Mo, W, Re, Zn, Cr, Mn, Ce, or Ga (paragraph [0039]). When the metal is selected from these metals, the catalyst comprises 0 wt% Groups 8-10 metals, which is within the range of less than 0.1 wt% of instant claim 42. Sattler further teaches that the catalyst also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the dehydrogenation catalyst of Sattler in the process of Heckelsberg, because each of Heckelsberg and Sattler teaches a dehydrogenation catalyst for dehydrogenation of propane, and Sattler teaches that the catalyst comprising tin in the framework and the additional metal also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
With regard to the amount of tin ii), Chen teaches a dehydrogenation process of paraffins having 2-30 carbon atoms (column 7, lines 41-42) comprising a catalyst including a zeolite comprising tin incorporated in the framework (column 1, lines 17-22). Chen teaches that the tin is included in the zeolite in a molar fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Chen further teaches that the catalyst comprising tin in the framework in this amount has increased selectivity and conversion (column 9, lines 22-24).
Using molar mass to convert the mole fractions to weights, Chen teaches 1.3 to 42.6 wt% tin in the zeolite. Sattler teaches that the catalyst comprises 2 to 80 wt% binder (paragraph [0067]) and 0.1 to about 3 wt% catalytic metal (paragraph [0037]), where the 17 to 97.9 wt% remaining is the zeolite. Thus, using the amounts of Chen, the catalyst of Sattler can comprise 0.2 to 41.7 wt% tin, which overlaps the range of 3 to 15 wt% of instant claim 24, rendering the range prima facie obvious.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the amount of tin in the catalyst of Chen for the catalyst of Sattler, because each of Heckelsberg and Chen teaches a dehydrogenation catalyst comprising platinum on a support for dehydrogenation of propane, and Chen teaches that the catalyst having a zeolite incorporating tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
With regard to the selectivity iii), Heckelsberg in view of Chen does not explicitly teach the propane selectivity to C2-C4 olefins is at least about 55 wt%. However, Heckelsberg in view of Sattler and Chen teaches a similar dehydrogenation catalyst comprising tin in the framework in a similar amount, the same metathesis catalyst, and teaches dehydrogenation and metathesis using the same feed comprising propane in an amount within the claimed range of at least 20 vol%. Thus, one of ordinary skill in the art would reasonably expect a similar result of selectivity to C2-C4 olefins of at least about 55 wt%, as claimed, absent any evidence to the contrary.
With regard to claims 28 and 43, Heckelsberg teaches a method of dehydrogenation of propane and disproportionation of the resulting propylene using a combined dehydrogenation-disproportionation catalyst as a physical mixture (catalyst system B instant claim 28) (column 1, lines 49-54). When the feed is pure propane as described in Heckelsberg (column 3, line 75), the feed comprises 100 vol% propane, which is within the range of at least about 20 vol% of instant claim 28. Heckelsberg teaches that the disproportionation catalyst comprises tungsten or molybdenum (Group 6) on a support (column 2, lines 21-24). Heckelsberg teaches the general dehydrogenation catalyst, and further teaches some examples of a dehydrogenation catalyst (column 1, lines 54-56).
Heckelsberg is silent regarding i) the dehydrogenation catalyst comprising tin (instant claim 28) and comprising less than 0.1 wt% Groups 8-10 metals and chromium (instant claim 40), ii) the amount of tin in the stannosilicate catalyst, and iii) the propane selectivity of the process to C2-C4 olefins.
With regard to the catalyst being a stannosilicate comprising tin i), Sattler teaches dehydrogenation of propane to propene in the presence of a small pore zeolite catalyst (paragraph [0028]) where the zeolite comprises Sn in the framework (paragraph [0031]) and a catalytic metal (paragraph [0037]) where the catalytic metal can be Ag, Au, Mo, W, Re, Zn, Mn, Ce, or Ga (paragraph [0039]). When the metal is selected from these metals, the catalyst comprises 0 wt% Groups 8-10 metals and chromium, which is within the range of less than 0.1 wt% of instant claim 43. Sattler further teaches that the catalyst also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the dehydrogenation catalyst of Sattler in the process of Heckelsberg, because each of Heckelsberg and Sattler teaches a dehydrogenation catalyst for dehydrogenation of propane, and Sattler teaches that the catalyst comprising tin in the framework and the additional metal also removes hydrogen, thus affecting the reaction quotient and driving the reaction forward to additional dehydrogenation (paragraphs [0028] and [0002]).
With regard to the amount of tin ii), Chen teaches a dehydrogenation process of paraffins having 2-30 carbon atoms (column 7, lines 41-42) comprising a catalyst including a zeolite comprising tin incorporated in the framework (column 1, lines 17-22). Chen teaches that the tin is included in the zeolite in a molar fraction of 0.01 to about 0.49, aluminum in a fraction of 0.01 to 0.49, and silicon in a fraction of 0.5 (column 2, lines 29-35). Chen further teaches that the catalyst comprising tin in the framework in this amount has increased selectivity and conversion (column 9, lines 22-24).
Using molar mass to convert the mole fractions to weights, Chen teaches 1.3 to 42.6 wt% tin in the zeolite. Sattler teaches that the catalyst comprises 2 to 80 wt% binder (paragraph [0067]) and 0.1 to about 3 wt% catalytic metal (paragraph [0037]), where the 17 to 97.9 wt% remaining is the zeolite. Thus, using the amounts of Chen, the catalyst of Sattler can comprise 0.2 to 41.7 wt% tin, which overlaps the range of 3 to 15 wt% of instant claim 28, rendering the range prima facie obvious.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the amount of tin in the catalyst of Chen for the catalyst of Sattler, because each of Heckelsberg and Chen teaches a dehydrogenation catalyst comprising platinum on a support for dehydrogenation of propane, and Chen teaches that the catalyst having a zeolite incorporating tin in the framework has increased selectivity and conversion (column 9, lines 22-24).
With regard to the selectivity iii), Heckelsberg in view of Chen does not explicitly teach the propane selectivity to C2-C4 olefins is at least about 55 wt%. However, Heckelsberg in view of Sattler and Chen teaches a similar dehydrogenation catalyst comprising tin in the framework in a similar amount, the same metathesis catalyst, and teaches dehydrogenation and metathesis using the same feed comprising propane in an amount within the claimed range of at least 20 vol%. Thus, one of ordinary skill in the art would reasonably expect a similar result of selectivity to C2-C4 olefins of at least about 55 wt%, as claimed, absent any evidence to the contrary.
Conclusion
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/Alyssa L Cepluch/Examiner, Art Unit 1772
/IN SUK C BULLOCK/Supervisory Patent Examiner, Art Unit 1772